Heterobimetallic heterocyclic derivatives of indium(III)

Reactions of InCl₃ with potassium salts of bifunctional tridentate (L¹H₂HOC₆H₄CH NCH₂CHMeOH) and monofunctional bidentate (L²HHOC₆H₄CHN-i-Bu) Schiff bases in 1:1 and 1:2 molar ratio in benzene afford complexes In(L¹)Cl and In(L²)₂Cl, respectively. On reaction with potassium isopropoxymetallates KB(O-i-Pr)₄, KAl(O-i-Pr)₄, KTi(O-i-Pr)₅, and KNb(O-i-Pr)₆, they produce interes- ting heterobimetallic heterocyclic complexes. These are characterized by elemental (N, B, Al, Ti, and Nb) analyses, molecular weight measurements, and spectral [IR, NMR (¹H, ¹³C, ¹¹B, and ²⁷Al)] studies. Probable structures are suggested for them. © 2003 Wiley Periodicals, Inc. 15:21–25, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10206     

Radiochromatography of indium (111In) oxine

A paper chromatographic procedure is described for distinguishing complexed and uncomplexed indium in solutions resulting from the extraction of indium-111 with oxine (8-quinolinol).     

A mononuclear indium(I) carbene analogue

The 'one pot' reaction between K[N(SiMe(3))(2)], InI and the beta-diimine ligand precursor [H(NDippCMe)(2)CH](Dipp = C(6)H(3)Pr(i)(2)-2,6) gave [In[(NDippCMe)(2)CH]], the first example of a two-coordinate, neutral, In(i) singlet 'carbene analogue'.     

Direct preparation of allylic indium(III) reagents from allylic alcohols via a reductive transmetalation of pi-allylnickel(II) with indium(I) iodide

InI-mediated direct allylation of carbonyl compounds with allylic alcohols proceeded smoothly with catalytic amounts of Ni(acac)(2) and PPh(3) to give the corresponding homoallylic alcohols in high yields. Allylindium compounds were shown to be the real allylating agents in the present system. Substituted allylic alcohols gave branched homoallylic alcohols with syn-selectivity irrespective of the geometry of the starting allylic alcohols, whereas high anti-selectivity was observed when a bulky substituent is present in the allylic alcohols. The outcome of the diastereoselectivity is discussed on the basis of the reaction mechanism, comparing with the corresponding Pd-catalyzed version. Another distinct behavior between the Ni- and Pd-catalyzed allylation was demonstrated in the reaction of hex-1,5-diene-3,4-diol derivatives: the Pd catalyst did not give any coupling product, whereas the Ni-catalyzed InI-mediated reaction with benzaldehyde afforded the 1:1 and 1:2 adduct diols selectively depending on the reaction conditions.     

X-ray diffraction study of scanium(III) and indium(III) tris(dipivaloylmethanates)

Conclusions An x-ray diffraction study was carried out for scandium(III) and indium(III) tris(di pivaloylmethanates). The similarity of the unit cell parameters, the reflection indices and analogous ratios of the intensities of the major lines in the diffraction patterns indicate the isostructural nature of Sc(DPM)₃ and In(DPM)₃ with Fe(DPM)₃.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2098–2099, September, 1987.     

Regioselective indium(III) trifluoromethanesulfonate-catalyzed hydrothiolation of non-activated olefins

Indium(III) trifluoromethanesulfonate was found to be an excellent catalyst for the highly regioselective intra- and intermolecular addition of thiols to non-activated olefins and could be recycled and reused without loss of activity.     

Crystal structure of indium(III) Schiff base complex

The title compound [In(C₂₂H₃₀N₄O₄)]Cl (I) bis[(N-salicylidene-N′-(2-hydroxyethyl)ethyleneediamine) indium(III) chloride is prepared, and its crystal structure is determined by single crystal X-ray diffraction at room temperature. The complex crystallizes in the monoclinic space group P2₁/n, a = 9.9704(6) ?, b = 24.9554(15) ?, c = 10.5707(6) ?, β = 116.46(2)°, V = 2354.6(2), Z = 4. The X-ray analysis reveals that the In^III ion is surrounded by four nitrogen and two oxygen atoms from two ligands leading to a distorted octahedral geometry. The molecule has the form of tongs at a junction point with the metal. Five membered rings adopt envelope conformation. In the crystal structure, the molecules are linked via N-H...Cl, O-H...O, O-H...Cl, and C-H...Cl intermolecular interactions. The structure is further stabilized by C-H...π (arene) interactions.     

Redox reactions involving the indium(III) catecholate complexes

Indium catecholate complexes 3,6-CatInR (3,6-Cat is the 3,6-di-tert-butyl-o-benzoquinone dianion (3,6-Q), R = Me (I) and Et (II)) are synthesized by the exchange reaction between RInI₂ and thallium catecholate 3,6-CatTl₂. Compounds I and II are trimeric in both the solution and crystalline state. The oxidation of compound I and earlier described complex [3,6-CatInI(THF)]₂ (THF is tetrahydrofuran) by various substrates (iodine, 3,6-Q, and tetramethylthiuram disulfide) is studied. Different indium(III) o-semiquinone complexes are the reaction products, depending on the reaction conditions.     

Electrochemical and spectroelectrochemical properties of tetra-tert-butylphthalocyanine indium(III)

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Synthesis of indium(iii) acetylacetonate by electrochemical dissolution

Russian Chemical Bulletin - A single crystal of indium(iii) acetylacetonate (In(acac)3) was obtained by alternating-current electrochemical dissolution of indium metal in the presence of...     

Tris(difluoro and trifluorobutane-2,4-dionato) gallium(III) and indium(III) complexes

Eight tris(β-diketonate)gallium(III) and seven tris(β-diketonate)-indium(III) complexes M(RCOCH-COR′)₃, with R′being difluoromethyl and trifluoromethyl substituents and R′ being methyl, phenyl, aryl, 2′-naphthyl and 2′-thienyl substituents have been studied by nuclear magnetic resonance spectroscopy. The complexes are all nonrigid (fluxional) and their ¹⁹F NMR spectra show four resonances in the nonexchanging regions due to cis and trans isomers. A variable low temperature study of these complexes was done for the gallium chelates and activation parameters are calculated. The indium complexes all have nonexchanging regions below ?100°C. The ¹³C NMR data on the complexes are also reported.     

Synthesis and characterization of (octaaryltetraazaporphyrinato)indium(III) complexes for optical limiting

The preparation of (octaaryltetraazaporphyrinato)indium(III) chlorides [aryl = phenyl (5a), p-tert-butylphenyl (6a), p-(trifluoromethyl)phenyl (7a), m-(trifluoromethyl)phenyl (8a)] and their reactions with aryl Grignard reagents XMgBr to give 5b-8b [X = p-(trifluoromethyl)phenyl] and 5c (R = 3,5-difluorophenyl) are described. The characterization of all compounds by UV-vis, FT-IR, and (1)H and (13)C NMR spectroscopy was performed. The hypsochromic shift of all bands in the absorption spectra of complexes 5a-8a is observed in the sequence 6a < 5a < 7a approximately 8a. This is associated with the increasing electron-withdrawing character of the aryl substituents in the periphery of the tetraazaporphyrin macrocycle. Compounds 8a,b are very good soluble in organic solvents with 8a exhibiting the higher photochemical stability among the various synthesized species. The optical limiting (OL) properties of the complexes have been studied and correlated with the structure of the (tetraazaporphyrinato)indium(III) complexes and the electronic nature of the different substituents. In particular, the OL effect at 532 nm increases on going from the series of compounds 5 to the series 8.     

Conversion of methanol to 2,2,3-trimethylbutane (triptane) over indium(III) iodide

InI3 is able to catalyze the conversion of methanol to a mixture of hydrocarbons at 200 degrees C with one highly branched alkane, 2,2,3-trimethylbutane (triptane), being obtained in high selectivity. The mechanism for InI3-catalyzed reactions appears to be basically the same as that proposed for the previously studied ZnI2-catalyzed system in which sequential methylation of olefins is followed by competing reactions of the resulting carbocation: proton loss to give the next olefin vs hydride transfer to give the corresponding alkane. Although the reaction conditions and typical triptane yields achievable with ZnI2 and InI3 are quite similar, the two systems behave rather differently in a number of important particulars, including significant differences between the detailed product distributions. Most of the differences in behavior can be ascribed to the stronger Lewis acidity of InI3, including the ability to activate some alkanes, the higher activity for methylation of arenes, and the fact that methanol conversion can be observed at somewhat lower temperatures with InI3 than with ZnI2.